Cupriferous azo dyestuffs



Patented Aug. 23, 1938 UNITED STATES PATENT OFFICE C-UPRIFEROUS AZO- DYESTUFFS poration of Delaware No Drawing. Application July 14, 1936, Serial No. 90,614. In Germany August 10, 1935 5 Claims.

The present invention relates to azo dyestuffs containing copper in a complex form, more particularly it relates to azo dyestuffs which may be represented by the general formula:

In the said general formula R1 represents the radical of a diazotizationcomponent of the henzene or naphthalene series, R2 stands for the radical of a middle-component of the benzene or naphthalene series, R3 stands for the radical of a middle-component of the benzene series, R4 stands for a radical of the benzene series, bearing the azo group in metaor para-position to the carbonyl group, R5 stands for the radical of a dihydroxy compound of the benzene or naphthalene se ries, bearing the azo groups in orthopositions to the hydroxy groups and R6 stands for the radical of a diazotization compound suitable for yielding azo dyestuffs capable of forming metal complex compounds.

Suitable dihydroxy compounds of the benzene or naphthalene series capable of coupling twice v are for instance 1,3-dihydroxy-benzene, 1,3-dihydroxybenzene-4-carboxylic acid, 2,6-dihydroxybenzoylamino disazo compound of the general formula:

R1-N=N-R2N=NRa-NHC OR4NH1 wherein R1, R2, R3 and R4 mean the same as stated above, may be combined with the dihydroxy compound capable of coupling twice and the product then coupled with the diazo. compound suitable for yielding azo dyestuffs capable of forming heavy metal complex compounds, whereupon the formation of the copper complex may be effected, or the said diazo-benzoylamino disazo compound may be caused to react upon the already formed, and if desired, coppered monoazo dyestuff from the dihydroxy compound and the diazo compound, and then, if not previfollowing formula:

CH CH:

the diazo compounds of o-aminohydroxy, oaminoalkoxy, o-aminohalogen compounds and oaminocarboxylic acids.

All components employed for the manufacture of the dyestuffs may contain substituents. In particular the dyestuffs may contain groups causing solubility, such as for instance sulfonic or carboxylic acid groups, which may suitably be present in the initial component R1, the first middle component R2 and/or in the diazo compound suitable for yielding azo dyestuffs which are capable of forming heavy metal complex compounds.

Our new dyestuffs may be built up in various manners. Thus, for instance, first the diazoare dissolved in 28000 parts by weight of water and 69 parts by weight of sodium nitrite. This solution is added, While stirring well, to a mixture of 300 parts by weight of hydrochloric acid of B. and ice water. After some time diazotization is complete. The suspension of the diazo compound is then added to a solution alkaline with sodium carbonate of 310 parts by weight of the monoazo dyestufi from 2-amino-l-hydroxybenzene-l-sulfonic acid and resorcin. After coupling is complete, the tetradisazo dyestuff formed is heated with a solution of 250 parts by weight of crystallized copper sulfate in 1500 parts by weight of water and 300 parts by weight of ammonia of 20% strength for about hour at 80-85 C. Finally the dyestuff is salted out, isolated and dried as usual.

Example 2 768 parts by weight of the p-aminobenzoylamino disazo dyestuff of the formula:

OCH:

H O a S I The dyestuff, having in its free state the following formula:

CH3 CH3 are diazotized as described in Example 1 and combined with the solution alkaline with sodium is a dark powder which dissolves in water with a brown coloration, in concentrated sulfuric acid with a violet coloration. The dyeings on cotton are of a beautiful yellowish brown, which is fast to light and unaffected by brightening. The dyestuff possesses the further property of dyeing equally mixed tissues of cotton and viscose.

Instead of coupling the diazotized p-aminobenzoyl-amino disazo dyestuif with the monoazo dyestuff from 2-amino-1-hydroxybenzene-4-sulfonic SOaH CH3 OaH carbonate of 374 parts by weight of the monoazo dyestuff from 2'chloro-l-amino-benzene-S-sulfonic acid and 1.3 dihydroxy-benzene copperedaccording to U. S. Patent No. 1,957,580. When coupling is complete, the dyestuff is salted out and dried.

The dyestuff having in its free state the following formula:

is a dark powder, which dissolves in water with a brown coloration. It dyes cotton brown shades, which are more red than those of the dyestufi of Example 1 and which are fast to light.

The aminobenzoyl compound of the above for- I mula may also be replaced by the corresponding m-aminobenzoyl compound. Dyestuffs of similar properties are thus obtained.

. Example 3 '804 parts by weight of the aminobenzoylaminodisazo dyestuff of the following formula:

CH3 CH3 fonic acid of the example may likewise be replaced by other aminophenol sulfonic acids, such as for instance by 2-amino-4-nitrophenol-6- sulfonic acid or 2-amino-6-nitrophenol-4-sulfonic acidor chloro-o-aminophenol sulfonic acids or o-aminocresol sulfonic acids. Instead of oaminophenol sulfonic acids likewise o-aminobenzoic acids may be employed.

Instead of combining the dihydroxy compound capable of coupling twice, such as for instance resorcin, first with the diazo compound, the diazotized p-aminobenzoylamino disazo dyestuif may first be combined with resorcin and the product then coupled with the diazo compound suitable for the copper complex formation, such as for instance 2 -amino- 1 -methoxybenzene- 4 -sulfonic acid, and the dyestufi finally converted into the copper compound.

are dissolved in 20000 parts by weight of water, and- 80 parts by weight of sodium nitrite are added. The solution is cooled with ice to 0-5 C. and acidified with 500 parts by weight of hydrochloric acid of 20 Be. while stirring. After a little time the diazo compound is poured into the solution of 395 parts by weight of the monoazo dyestuff from diazotized l-chloro-Z-aminophenol and 1,G-dihydroxynaphthalene-3-sulfonic acid, the solution containing an excess of sodium carbonate. After coupling is complete the dyestuff is isolated. It is then converted into its copper compound in the usual manner. This copper compound is a. dark powder, which easily dissolves in Water with a brown coloration. Cellulose fibers are dyed in a bath containing Glaubers salt and sodium carbonate dark brown shades.

The dyestufi corresponds in itsfree state to the following formula:

s0SH CH; OH: OH

N=NON=N NHCOON=N ven'tionand the shades obtained therewith on 10' cotton.

5 HOaS- 10 In the annexed table there are shown further dyestuffs prepared in accordance with the inw w w m H m m m M W S w n n 11m ww o a m mwwm 0 0 0 0 m 0 s Y D D B Y D D D D m D H H m H H H m m 0 0S 0 m m m It v m "m m S. a 0 H S {S S S a H S w S a w m m S n H H S I HS S S H We mg mg HQ H G S H mm w m N N N S /o 0 mm 7 m .m m m m m m m m S N. H H H mu m H H S H H m m m m m H mm 0 0 JV 0 0 0 0 S 0 O 0 c .m S I I H H S F. 0 0 0 0 0 0 0 w w w m m m H m m m m m m m S S H N N U. N N S N N N N. N m m m S w v v m 0 0 o m ow m to 0 n o 0 Lo m w w w w w w w w c o c A 0 o G c 0 0 0 0 m m m wtm v m m m S m m S. S. S: S. S S. a S H H H S H H N N N N N N N N v N N. m dmm m S S I mmam H H m m m H H H H m m mm 0 c C C C C1 O G 0 C 0 S H H H H H m m S S S. S m m N N N N N N N m m m m mmmm lm m SH m S v m m S m S S H. a m S- S m HG S w m m S. H S. H S. H S H S m N m S m m N m S S H H v S H I S S m H H H H N N N w H H H o N S .N H O H v S N H N H N H M w m H H a a m S w I m S S S S S. S H S H S H. D 0 I SI 0 s 0 0 0 0 w w 0 H o H H H H s w w m w m w m w M W Second middle Flrst middle component to i I Diazo compound ofg gggg giefiafllallllldofguii Amiuoaroylatmg agent Fmal g%;% ;g3% g 2 of Shade dmzotlzed ther diazotized S 03H $113 (I311 I\T02 NE; NH: C -NHQ G10 O-QNHZ OOH-I-HzN S 0311 S 03H s 0311 cm on s 0311 NH; NH: Own 01o 0-NH2 OOH+HZN Do H o3s 0H sozn nna (3H3 on s 03H NIH: O-Nm G-NH: 01o 0,NH WOH+HN- Brown I H 038- O H S 0311 s 03H (3H3 (IJHZ on NH: ONE, NHa 01o 0 -NHz s 03H B gislfi I H 03s OH+H:;N s 03H I OH s 03H (3H3 (3E3 011 NH: ONE: ONE; 010 OC NH:

H038 OH+HzN S 05H H S 0311 ICE: (EH8 ONE; Gnu, C10 o-G-nm H035 SOaH s OH+HZNQ We claim:

1. A20 dyestuffs containing copper in a complex form of the general formula:

R1N=N-Rz-N=N-RaNHC OR N=N-R5 N= Ra wherein R1 represents a member selected from the group consisting of radicals of diazotization components of the benzene and naphthalene series, R2 stands for a member selected from the group consisting of radicals of middle-components of the' benzene and naphthalene series, R3 stands for the radical of a middle component of the benzene series, R4 stands for a radical of the benzene series, bearing the azo group in one of the positions meta and para to the carbonyl group, R5 stands fora member selected from the group consisting of radicals of dihydroxy compounds of the benzene and naphthalene series, bearing the azo groups in ortho-positions to the hydroxy groups, and Rs stands for the radical of a diazotization compound suitable for yielding azo dyestuffs capable of forming complex compounds, said azo dyestuffs yielding in general on vegetable fibers brown shades of good fastness to light.

SOaH

2. Azo dyestuffs containing copper in a complex form of the general formula:

wherein R1 represents a member selected from the group consisting of radicals of diazotization components of the benzene and naphthalene series, R2 stands for a member selected from the group consisting of radicals of middle-components of the benzene and naphthalene series, R3 stands for the radical of a middle component of the benzene series, R4 stands for a radical of the benzene series, bearing the azo group in one of the positions meta and para to the carbonyl group, R5 stands for the radical of resorcin, and Rs stands for the radical of a diazotization compound suitable for yielding azo dyestuffs capable of forming complex compounds, said azo dyestufis yielding in general on vegetable fibers brown shades of good fastness to light.

3. A dyestufi having in its free state the following formula:

yielding on vegetable fibers yellowish-brown shades of good fastness to light.

5. Dyestufis having in their free state the following general formula:

10 s 03H CH3 4. A dyestuif having in its free state the followyielding on vegetable fibers yellowish-brown 15 ing formula: shades of good fastness to light.

yielding on vegetable fibers yellowish-brown 25 shades of good fastness to light.

DETLEF DELFS.

RUDOLF KNOCHE. 

